CN111019102A - Method for preparing titanium-based polyester by DMT method - Google Patents
Method for preparing titanium-based polyester by DMT method Download PDFInfo
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- CN111019102A CN111019102A CN201911413991.5A CN201911413991A CN111019102A CN 111019102 A CN111019102 A CN 111019102A CN 201911413991 A CN201911413991 A CN 201911413991A CN 111019102 A CN111019102 A CN 111019102A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
Abstract
The invention relates to a method for preparing titanium-based polyester by a DMT method, which comprises the following steps: mixing DMT, EG, polyester titanium catalyst composite material system and ester exchange catalyst, and then carrying out esterification reaction and polycondensation reaction to obtain titanium-based polyester; the polyester titanium catalyst composite material system mainly comprises a polyester prepolymer with the polymerization degree of 5-30, a sheet-shaped titanium polyester catalyst dispersed in the polyester prepolymer and a phosphorus stabilizer. According to the method for preparing the titanium-based polyester by the DMT method, the polyester prepolymer with the polymerization degree of 5-30 is adopted to wrap the sheet-shaped titanium-based polyester catalyst with excellent hydrolysis resistance, and the polyester titanium-based catalyst composite material is only melted at a high temperature to release the titanium-based polyester catalyst, so that the hydrolysis reaction of the titanium-based polyester catalyst caused by water contained in the storage and transportation process can be reduced or even avoided, the high dispersibility and high activity of the titanium-based polyester catalyst are ensured, and the yellowing of the titanium-based polyester is reduced.
Description
Technical Field
The invention belongs to the technical field of polyester fibers, and relates to a method for preparing titanium-based polyester by a DMT method.
Background
Polyester fibers, the largest variety of synthetic fibers, have been leading the chemical fiber market. In particular, polyethylene terephthalate (PET) among polyester fibers has various excellent properties and is widely used, and therefore, unless otherwise specified, the polyester fibers are mostly PET fibers.
PET can be produced by using DMT as a raw material through ester exchange, and then by polymerization, the PET is also called DMT method because DMT is used as a raw material.
Since ICI company in England invented polyester in 1947, the production of polyester mainly uses antimony compound as catalyst, such as Sb2O3 or antimony acetate, the antimony catalyst has the advantages of high activity, low price and small promotion effect on side reaction, so the application is wide, and 90% of the polyester devices in the world currently adopt the antimony catalyst. However, since the antimony-based catalyst is harmful to the human body and pollutes the environment during processing, a new non-antimony-based catalyst is required to replace the original antimony-based catalyst.
The titanium catalyst is generally applied to the direct esterification and continuous polycondensation polyester process, has the advantages of environmental protection, safety, high efficiency, great reduction of the temperature in the synthesis and spinning process and reduction of energy consumption, and can also make the physical and mechanical properties of the fiber more uniform, improve the stability in the production process and reduce the consumption of materials.
Commercial titanium-based catalysts include two broad classes: 1) the compound/dispersion liquid of the catalyst and the glycol is in a liquid state, such as: the catalyst has poor long-term stability and dispersion performance, so that the catalyst can generate agglomeration and particle enlargement phenomena in the transportation and storage processes, can influence the catalytic activity due to hydrolysis, is easy to deteriorate, and can generate hydrolysis reaction to a greater extent at the high temperature of the synthesized polyester to destroy the catalytic activity of the catalyst; 2) the solid powder of the catalyst is introduced into a polyester synthesis system by preparing an ethylene glycol dispersion liquid during application, the catalytic activity of titanium element is generally regulated by introducing a certain proportion of Si element, and the particle size is designed to be micron-sized so as to inhibit the agglomeration of particles, but the catalyst still has the following defects: firstly, because the particle size of the solid catalyst is further increased undoubtedly when compounds of other elements such as Si element are introduced, the particle size of the catalyst is larger, and the dispersibility is not good; secondly, in order to improve the dispersion effect of the solid catalyst, methods such as surface modification and the like have complex process and higher cost; thirdly, hydrolysis reaction can occur to a large extent at high temperature for synthesizing polyester, so that the catalytic activity of the catalyst is destroyed; 3) the product prepared by the catalyst has poor thermal stability, yellow color at high temperature and high b value.
Therefore, the research on a method which can avoid the hydrolysis reaction of the polyester catalyst, improve the stability and the dispersibility of the polyester catalyst and reduce the yellowing of the finally prepared titanium-based polyester is of great significance.
Disclosure of Invention
The invention aims to solve the problems that polyester catalysts in the prior art are poor in dispersity and easy to cause yellowing, and provides a method for preparing titanium-based polyester through a DMT method.
In order to achieve the above purpose, the invention adopts the following scheme:
a DMT method for preparing titanium-based polyester, mix DMT (dimethyl terephthalate), EG, polyester titanium catalyst composite material system and ester exchange catalyst, take esterification and polycondensation reaction to make titanium-based polyester;
the polyester titanium catalyst composite material system mainly comprises a polyester prepolymer with the polymerization degree of 5-30, a sheet-shaped titanium polyester catalyst dispersed in the polyester prepolymer and a phosphorus stabilizer.
When the traditional process is adopted for preparing polyester, the catalyst is often easy to agglomerate before being added into a reaction kettle due to poor dispersion performance, so that the catalytic activity is influenced, and the catalyst is easy to deteriorate, in order to avoid agglomeration of the catalyst, the generally adopted method is to regulate the catalytic activity of titanium element by introducing a certain proportion of Si element, and the particle size is designed to be micron order, so as to inhibit agglomeration of particles, however, the methods have the following problems:
1) because the particle size of the solid catalyst is undoubtedly further increased when compounds of other elements such as Si element are introduced, the particle size of the catalyst is larger, and the dispersibility is poor; 2) in order to improve the dispersion effect of the solid catalyst, methods such as surface modification and the like have complex process and higher cost; 3) the catalyst can generate hydrolysis reaction to a large extent at high temperature for synthesizing polyester so as to destroy the catalytic activity of the catalyst;
the catalyst is wrapped by the polyester prepolymer with the polymerization degree of 5-30, so that agglomeration is effectively avoided, the problems are solved, the polyester prepolymer has a high melting point, and only melts at a high temperature to release the catalyst in the polyester synthesis process, so that the secondary agglomeration phenomenon in the transportation or storage process can be avoided, and meanwhile, the polyester prepolymer is an intermediate for preparing a polyester high polymer and has excellent intrinsic compatibility with an intermediate system for synthesizing the high polymer, so that the polyester prepolymer can show high dispersibility in the polyester synthesis process;
the reaction temperature is higher in the process of synthesizing polyester by adopting a DMT method, the catalytic activity of the catalyst is higher under the high-temperature condition, side reactions are more, yellowing is easily caused, and when a common titanium compound is used for catalysis, the catalyst has stronger catalytic activity compared with an antimony catalyst, but when the titanium compound is degraded by thermal oxidation to form hydroxylation, the phenolic hydroxyl group is more easily converted into a quinoid structure by the titanium compound, so that obvious PET color yellowing is caused; according to the invention, the flaky titanium polyester catalyst and the phosphorus stabilizer are matched with each other, so that the thermal stability of a reaction system is improved, the occurrence of side reactions is reduced, and further yellowing can be reduced; meanwhile, the organic composition in the sheet titanium polyester catalyst has an inhibiting effect on the phosphorus stabilizer and the titanium element in the catalyst, so that the influence on the activity of the catalyst can be reduced;
in addition, when the polyester is prepared by adopting the traditional DMT method, the catalyst is generally added into a pre-polycondensation kettle after the esterification reaction is finished, the main reason is that the catalyst is easy to hydrolyze under the action of the high-temperature esterification reaction and water generated by the high-temperature esterification reaction to reduce or even lose the catalytic activity, however, the catalyst also has the esterification catalytic action although mainly playing the polycondensation catalytic action, and the catalyst cannot play the esterification catalytic action and cannot fully play the effect of the catalyst after the esterification reaction is finished;
the catalyst can be added in the esterification reaction stage or after the esterification reaction, can play roles of esterification catalysis and polycondensation catalysis, and has the main reason that the catalyst is a sheet titanium polyester catalyst which has excellent hydrolysis resistance, and a polyester prepolymer with the surface coated and the polymerization degree of 5-30 can avoid the agglomeration of the catalyst before the polyester prepolymer is added into a polymerization system, so that the problem of poor dispersibility is solved, and the catalyst can be melted in the esterification reaction process to release and be subjected to esterification catalysis.
As a preferred technical scheme:
the DMT method for preparing the titanium-based polyester comprises the following specific steps:
(1) mixing a DMT, EG, polyester titanium catalyst composite material system and an ester exchange catalyst, and then carrying out esterification reaction to obtain BHET (bis-hydroxyethyl terephthalate), wherein the esterification reaction is carried out in a nitrogen atmosphere, the pressure is 150-250 KPa, the temperature is 175-235 ℃, and the time is 110-130 min;
(2) conveying BHET into a pre-polycondensation kettle for pre-polycondensation reaction to obtain a pre-polycondensation product, wherein the pressure of the pre-polycondensation reaction is 100-10 KPa, the temperature is 235-270235-270 ℃, and the time is 5-50 min;
(3) conveying the pre-polycondensation product to a final polycondensation kettle for final polycondensation to obtain a titanium-based polyester melt, wherein the pressure of the final polycondensation reaction is 150-200 Pa, the temperature is 270-284 ℃, and the time is 70-80 min;
(4) and cooling and dicing the titanium-based polyester melt to obtain the titanium-based polyester chip.
In the step (1), the molar ratio of DMT to EG is 1: 2.1-2.5, and the adding amount of the sheet titanium polyester catalyst contained in a polyester titanium catalyst composite material system in the esterification reaction process is 4-6 ppm of the theoretical mass of the titanium-based polyester, and in the traditional process, the adding amount of the titanium catalyst is about 10-60 ppm of the theoretical mass of the titanium-based polyester due to the problems of dispersibility and hydrolysis resistance, and the comparison shows that the adding amount of the catalyst is obviously reduced because the polyester titanium catalyst composite material system can only be melted at a higher temperature to release the titanium catalyst, so that the hydrolysis reaction of the titanium catalyst caused by water contained in the storage and transportation process can be reduced or even avoided, and the catalyst is the sheet titanium polyester catalyst, the hydrolysis resistance is excellent, and hydrolysis reaction caused by water generated by esterification reaction can be avoided; the addition amount of the ester exchange catalyst is 300-500 ppm of the theoretical mass of the titanium-based polyester, and the ester exchange catalyst is magnesium acetate, manganese acetate, calcium acetate, zinc acetate or trivalent rare earth compounds (specifically cerium trichloride and lanthanum chloride);
in the step (3), the intrinsic viscosity of the titanium-based polyester melt is 0.64-0.68 dL/g, the chroma L value of the titanium-based polyester resin obtained by sampling from the titanium-based polyester melt is 60-65, the b value is 2-4, the chroma L value of the polyester melt prepared by the traditional process is generally 58-62, and the b value is generally 1-3.
The method for preparing the titanium-based polyester by the DMT method further comprises a toner, wherein the mass contents of the sheet-shaped titanium-based polyester catalyst, the phosphorus-based stabilizer and the toner in the polyester-titanium-based catalyst composite material system are respectively 0.5-20 wt%, 5-15 wt% and 0.5-8 wt%; the stabilizer and the toner are not required to be added, and can be selected not to be added, the stabilizer is generally added after the esterification reaction and before the pre-polymerization reaction when the polyester is synthesized by adopting the traditional process, the sheet-shaped titanium polyester catalyst, the stabilizer and the toner are firstly introduced into the synthesis process of the prepolymer to prepare the polyester titanium catalyst composite material system, and then the polyester titanium catalyst composite material system is introduced into the reaction system of the polyester, and the stabilizer does not need to be added again, so the operation convenience is improved.
The DMT method for preparing the titanium-based polyester has the structural general formula of Tix(ORO)y(OOC6C4H4COO)zH4Wherein R is C2～C4Z is more than or equal to 1, y + z is 2x +2, x is 4, the flaky titanium polyester catalyst is in a lamellar structure, and the thickness of the lamellar is 100-200 nm;
the preparation method of the sheet titanium polyester catalyst comprises the following steps: taking terephthalic acid or terephthalate, titanate and dihydric fatty alcohol as raw materials, carrying out reaction in stages under the conditions that the temperature is 150-280 ℃ and the pressure is 0.01-0.4 MPa, specifically comprising the steps of controlling the temperature to react for 0.5-2.0 h under the condition that the temperature is 150-250 ℃, then heating to 200-280 ℃ to continue the reaction, stopping the reaction when the degree of esterification or ester exchange reaches 70-90%, filtering while hot, and crushing and grinding the obtained solid product to prepare the sheet-shaped titanium polyester catalyst;
the terephthalic acid ester is dimethyl terephthalate, diethyl terephthalate, dihydroxyethyl terephthalate, dihydroxypropyl terephthalate or dihydroxybutyl terephthalate; the titanate is n-butyl titanate, tetraisopropyl titanate or ethyl titanate; the dihydric fatty alcohol is ethylene glycol, 1, 3-propylene glycol or 1, 4-butanediol;
the phosphorus stabilizer is more than one of trimethyl phosphate, triethyl phosphate, tripropyl phosphate, triisopropyl phosphate, tributyl phosphate, triphenyl phosphate, tripropyl phosphate, phosphoric acid and phosphorous acid;
the toner is a bluing agent (e.g., Issman chemical OB-1, Clainen, Germany, solvent blue 45, Ciba Irganox 1425, Ciba Irgamod 195, Germany) or a reddening agent (e.g., Poulvan OnColoredgeglo, Clariant, Germany, Red GFP).
The preparation method of the polyester titanium catalyst composite material system comprises the following steps: and melting and blending the solid polyester prepolymer with the polymerization degree of 5-30 with a sheet-shaped titanium polyester catalyst, a phosphorus stabilizer and a toner, and cooling to obtain a solid polyester titanium catalyst composite material system, wherein the melting and blending temperature is 100-270 ℃, and the time is 1.5-6 hours.
The preparation method of the polyester titanium catalyst composite material system comprises the following steps: adding an additive or a dihydric alcohol dispersion liquid of the additive into a polyester prepolymer melt with the polymerization degree of 5-30, uniformly stirring and cooling to obtain a solid or slurry polyester titanium catalyst composite material system, wherein the additive is a sheet titanium polyester catalyst, a phosphorus stabilizer and a toner, the sheet titanium polyester catalyst, the stabilizer and the toner can be directly added, or can be added after being dispersed in dihydric alcohol, or can be partially added directly, or can be partially added after being dispersed in the dihydric alcohol, the adding modes are all within the protection range of the invention, and when the adding mode is added after being dispersed in the dihydric alcohol, when the mass ratio of the polyester prepolymer to the dihydric alcohol is more than 1, the final product is in a solid state; when the mass ratio of the polyester prepolymer to the dihydric alcohol is 0.5-1, the final product is in a slurry state; the mass concentration of the dihydric alcohol dispersion liquid of the additive is 30-70 wt%, and the dihydric alcohol is ethylene glycol, 1, 3-propylene glycol or 1, 4-butanediol.
The preparation method of the polyester titanium catalyst composite material system comprises the following steps: a, B and C are mixed evenly and then are processed through esterification reaction, pre-polycondensation reaction and cooling to obtain a solid or slurry polyester titanium catalyst composite material system, wherein A is dibasic acid or dibasic acid ester, B is dihydric alcohol, C is additive or dihydric alcohol dispersion liquid of the additive, the additive is sheet titanium polyester catalyst, phosphorus stabilizer and toner, the sheet titanium polyester catalyst, the stabilizer and the toner can all adopt a direct adding mode, can also adopt a mode of adding the rest dihydric alcohol after being dispersed in the dihydric alcohol and then being supplemented, can also partly adopt a direct adding mode, and partly adopt a mode of adding the rest dihydric alcohol after being dispersed in the dihydric alcohol, and the adding modes are all within the protection scope of the invention. In the polyester synthesis process in the prior art, a sheet-shaped titanium polyester catalyst, a stabilizer and a toner are added before esterification reaction, and the sheet-shaped titanium polyester catalyst, the stabilizer and the toner are subjected to system environment changes such as temperature, pressure and the like, and physical and chemical reactions possibly occur among each other or between the sheet-shaped titanium polyester catalyst, the stabilizer and the toner and reaction monomers for preparing polyester, so that the catalytic activity of the sheet-shaped titanium polyester catalyst, the stabilizer and the toner is changed. The invention firstly introduces the sheet titanium polyester catalyst, the stabilizer and the toner into the synthesis process of the prepolymer to prepare a polyester titanium catalyst composite material system, and then introduces the polyester titanium catalyst composite material system into a polyester reaction system, and as the synthesis process of the prepolymer is similar to the esterification and polycondensation reaction of polyester synthesis, the catalytic activity and the efficiency of the polyester titanium catalyst composite material system can be further improved when the polyester titanium catalyst composite material system is used as a polyester catalyst after the esterification and pre-polycondensation reaction of the prepolymer; the esterification reaction is carried out in a nitrogen atmosphere, the pressure is 100-400 KPa, the temperature is 180-260 ℃, and the time is 2-2.5 h; the pressure of the pre-polycondensation reaction is 100-10 KPa, the temperature is 235-270260-270 ℃, and the time is 10-30 min.
In the DMT method for preparing the titanium-based polyester, the molar ratio of the sum of the molar amounts of the diols in B and C to A is 1-2: 1, when the molar ratio of the sum of the molar amounts of the diols in B and C to A is 1-1.5, the final product is in a solid state, and when the molar ratio of the sum of the molar amounts of the diols in B and C to A is more than 1.5, the final product is in a slurry state; the B is the same as the dihydric alcohol in the dihydric alcohol dispersion liquid of the additive, the mass concentration of the dihydric alcohol dispersion liquid of the additive is 35-70 wt%, and the mass of the sheet titanium polyester catalyst accounts for 10-20% of the sum of the mass of the dihydric alcohol in the B and the dihydric alcohol in the C.
The DMT method for preparing the titanium-based polyester comprises the steps of preparing a dibasic acid by using a dibasic acid, a dibasic acid by using a dibasic acid ester, a dibasic acid ester and a dibasic alcohol by using a dibasic acid ester, wherein the dibasic acid is terephthalic acid, isophthalic acid or isophthalic acid-5-sodium sulfonate, the dibasic acid ester is dimethyl terephthalate, and the dibasic alcohol is ethylene glycol, 1, 3-propanediol or 1, 4-butanediol.
Has the advantages that:
(1) according to the method for preparing the titanium-based polyester by the DMT method, the polyester prepolymer with the polymerization degree of 5-30 is adopted to wrap the sheet titanium-based polyester catalyst with excellent hydrolysis resistance, and the polyester titanium-based catalyst composite material is only melted at a high temperature to release the titanium-based polyester catalyst, so that the hydrolysis reaction of the titanium-based catalyst caused by water contained in the storage and transportation process can be reduced or even avoided;
(2) according to the method for preparing the titanium-based polyester by the DMT method, the sheet-shaped titanium-based polyester catalyst is wrapped by the polyester prepolymer with the polymerization degree of 5-30, the polyester prepolymer is an intermediate for preparing the polyester chip, and the polyester prepolymer has intrinsic good compatibility with an intermediate system of the synthesized polyester chip, so that the polyester chip is prevented from being agglomerated, and the high dispersibility and the high activity of the polyester catalyst are ensured;
(3) according to the method for preparing the titanium-based polyester by the DMT method, the activity of the catalyst is inhibited and yellowing is reduced by the mutual matching of the sheet-shaped titanium-based polyester catalyst and the phosphorus-based stabilizer.
Drawings
FIG. 1 is an infrared spectrum (FTIR spectrum) of a composite system of the polyester titanium based catalyst of example 7 of the present invention.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A preparation method of a sheet titanium polyester catalyst comprises the steps of mixing terephthalic acid, ethylene glycol and n-butyl titanate with a molar ratio of 1:1.5:0.01, reacting for 0.5h at 150 ℃ and under 0.01MPa, heating to 200 ℃, continuing to react until the esterification degree reaches 70%, terminating the reaction, filtering while hot, and crushing and grinding to obtain the sheet titanium polyester catalyst with the average particle size of 0.5 mu m.
Examples 2 to 6
A process for preparing the flaky Ti-series polyester catalyst includes such steps as mixing BT, CT and DT in mole ratio AT, reacting GT AT ET and FT, heating to HT, reacting until the esterification degree reaches IT, filtering, and pulverizing.
Example 7
A preparation method of a polyester titanium catalyst composite material system comprises the steps of firstly adding ethylene glycol dispersion liquid of a sheet-shaped titanium polyester catalyst with the mass concentration of 30 wt% into a polyester prepolymer (ethylene terephthalate prepolymer) melt with the polymerization degree of 5-8, and then uniformly stirring and cooling to obtain the polyester titanium catalyst composite material system, wherein the sheet-shaped titanium polyester catalyst is prepared from example 1, and the mass content of the sheet-shaped titanium polyester catalyst in the polyester titanium catalyst composite material system is 20 wt%.
0.1g of the polyester titanium catalyst composite system is dispersed in 30mL of water, after the mixture is heated and stirred for 3 hours at 70 ℃, the residual solid is washed by absolute ethyl alcohol and dried, and then the sample is subjected to FTIR characterization, as shown in figure 1, the crystal structure and characteristic groups of the sample of the polyester titanium catalyst composite system in the invention are not changed too much after the sample is treated by hot water, and the FTIR graph is also shown at 2924cm-1、2854cm-1Left and right CH2The vibration peak disappears, which indicates that the sample has better stability in water, and meanwhile, no stabilizer or toner is added in the above embodiment, so that the polyester titanium catalyst composite material system composed of the polyester prepolymer with the polymerization degree of 3-8 and the sheet titanium polyester catalyst has excellent stabilityAnd (5) performing qualitative determination.
Examples 8 to 12
A preparation method of a polyester titanium catalyst composite material system comprises the steps of firstly adding BN into a polyester prepolymer (ethylene terephthalate prepolymer) melt with the polymerization degree of AN, uniformly stirring and cooling to obtain the polyester titanium catalyst composite material system, wherein the BN contains additives, the additives comprise a titanium catalyst, a stabilizer and a toner, and the mass contents of the titanium catalyst, the stabilizer and the toner in the polyester titanium catalyst composite material system are CN, DN and EN.
Example 13
A preparation method of a polyester titanium catalyst composite material system comprises the steps of melting and blending a solid polyester prepolymer (ethylene terephthalate prepolymer) with the polymerization degree of 25-30, a sheet-shaped titanium polyester catalyst (catalyst), triisopropyl phosphate (stabilizer) and Germany Ciba Irganox 1425 (toner) at the temperature of 150 ℃ for 2 hours, cooling and crushing to obtain the polyester titanium catalyst composite material system, wherein the sheet-shaped titanium polyester catalyst is prepared from example 2, and the mass contents of the sheet-shaped titanium polyester catalyst, the triisopropyl phosphate and the Germany Ciba Irganox 1425 in the polyester titanium catalyst composite material system are respectively 18 wt%, 5 wt% and 4 wt%.
Examples 14 to 19
A preparation method of a polyester titanium catalyst composite material system comprises the steps of melting and blending a solid polyester prepolymer (ethylene terephthalate prepolymer) with polymerization degree of AS with a titanium catalyst, a stabilizer and a toner at the temperature of BS (styrene-butadiene-styrene) for CS, cooling and crushing to obtain the solid polyester titanium catalyst composite material system, wherein the mass contents of the titanium catalyst, the stabilizer and the toner in the polyester titanium catalyst composite material system are DS, ES and FS respectively.
Examples 20 to 24
A preparation method of a polyester titanium catalyst composite material system comprises the steps of uniformly mixing A, B and C, and then carrying out esterification reaction, pre-polycondensation reaction and cooling to obtain the polyester titanium catalyst composite material system, wherein A is dibasic acid (terephthalic acid, isophthalic acid or isophthalic acid-5-sodium sulfonate) or dibasic acid ester (dimethyl terephthalate), B is dihydric alcohol, C is an additive or a dihydric alcohol dispersion liquid of the additive, the additive is a titanium catalyst, a stabilizer and a toner, the molar ratio of the sum of the molar amounts of the dihydric alcohol in the B and the dihydric alcohol in the C to the molar amount of the dihydric alcohol in the A is 1-2: 1, B is the same as the dihydric alcohol in the glycol dispersion liquid of the additive (specifically ethylene glycol, 1, 3-propylene glycol or 1, 4-butanediol), the mass concentration of the dihydric alcohol dispersion liquid of the additive is 35-70 wt%, and the mass of the titanium catalyst accounts for 10-20% (D) of the sum of the mass of the dihydric alcohol in the B and the dihydric alcohol in the C, the esterification reaction is carried out in a nitrogen atmosphere, the pressure is 100-400 KPa, the temperature is 180-260 ℃, the time is 2.0-2.5 h, the pressure of the pre-polycondensation reaction is 100-10 KPa, the temperature is 260-270 ℃, the time is 10-50 min, and the mass contents of the titanium catalyst, the stabilizer and the toner in the polyester titanium catalyst composite material system are respectively 0.5-20 wt% (E), 5-15 wt% (F) and 0.5-8 wt% (G).
Examples 25 to 42
The titanium-based polyester is prepared by adopting the polyester titanium catalyst composite material system prepared in the embodiment X and a DMT method, and the specific steps are as follows:
(1) mixing a DMT, EG, polyester titanium catalyst composite material system and an ester exchange catalyst (A) and then carrying out esterification reaction to obtain BHET, wherein the esterification reaction is carried out under the nitrogen atmosphere, the pressure (P3) is 150-250 KPa, the temperature (T3) is 175-235 ℃, and the time (T3) is 110-130 min; wherein the molar ratio (molar ratio 2) of DMT to EG is 1: 2.1-2.5, the addition amount of a sheet-shaped titanium polyester catalyst contained in a polyester titanium catalyst composite material system in the esterification reaction process is 4-6 ppm of the theoretical mass (titanium content) of titanium-based polyester, and the addition amount of a transesterification catalyst is 300-500 ppm of the theoretical mass (addition amount 1) of titanium-based polyester;
(2) conveying BHET into a pre-polycondensation kettle for pre-polycondensation reaction to obtain a pre-polycondensation product, wherein the pressure (P4) of the pre-polycondensation reaction is 100-10 KPa, the temperature (T4) is 235-270 ℃, and the time (T4) is 5-50 min;
(3) conveying the pre-polycondensation product to a final polycondensation kettle for final polycondensation to obtain a titanium-based polyester melt, wherein the pressure (P5) of the final polycondensation is 150-200 Pa, the temperature (T5) is 270-284 ℃, and the time (T5) is 70-80 min; wherein the intrinsic viscosity of the titanium-based polyester melt is 0.64-0.68 dL/g, the chroma L value of the titanium-based polyester resin is 60-65, and the b value is 2-4;
(4) cooling and dicing the titanium-based polyester melt to obtain titanium-based polyester chips;
the parameters of examples 25 to 42 are shown in Table 1-2 below.
Example 43
A DMT process for preparing titanium based polyester substantially the same as in example 25 except that the polyester titanium based catalyst composite system and the amount thereof added in step (1) were changed to those in step (3), and the specific parameters thereof are shown in Table 2.
Table 1 parameters corresponding to examples 25 to 34
TABLE 2 parameters corresponding to examples 34 to 43
Claims (10)
1. A method for preparing titanium-based polyester by a DMT method is characterized in that: mixing DMT, EG, polyester titanium catalyst composite material system and ester exchange catalyst, and then carrying out esterification reaction and polycondensation reaction to obtain titanium-based polyester;
the polyester titanium catalyst composite material system mainly comprises a polyester prepolymer with the polymerization degree of 5-30, a sheet-shaped titanium polyester catalyst dispersed in the polyester prepolymer and a phosphorus stabilizer.
2. The DMT process of claim 1, wherein the process comprises the steps of:
(1) mixing a DMT, EG, polyester titanium catalyst composite material system and an ester exchange catalyst, and then carrying out esterification reaction to obtain BHET, wherein the esterification reaction is carried out in a nitrogen atmosphere, the pressure is 150-250 KPa, the temperature is 175-235 ℃, and the time is 110-130 min;
(2) conveying BHET into a pre-polycondensation kettle for pre-polycondensation reaction to obtain a pre-polycondensation product, wherein the pressure of the pre-polycondensation reaction is 100-10 KPa, the temperature is 235-270 ℃, and the time is 5-50 min;
(3) conveying the pre-polycondensation product to a final polycondensation kettle for final polycondensation to obtain a titanium-based polyester melt, wherein the pressure of the final polycondensation reaction is 150-200 Pa, the temperature is 270-284 ℃, and the time is 70-80 min;
(4) and cooling and dicing the titanium-based polyester melt to obtain the titanium-based polyester chip.
3. The method for preparing titanium-based polyester by using the DMT method as claimed in claim 2, wherein in the step (1), the molar ratio of DMT to EG is 1: 2.1-2.5, based on the mass of titanium element, the addition amount of the sheet-shaped titanium-based polyester catalyst contained in the polyester titanium-based catalyst composite material system in the esterification reaction process is 4-6 ppm of the theoretical mass of the titanium-based polyester, the addition amount of the ester exchange catalyst is 300-500 ppm of the theoretical mass of the titanium-based polyester, and the ester exchange catalyst is magnesium acetate, manganese acetate, calcium acetate, zinc acetate or a trivalent rare earth compound;
in the step (3), the intrinsic viscosity of the titanium-based polyester melt is 0.64-0.68 dL/g, the chroma L value of the titanium-based polyester resin is 60-65, and the b value is 2-4.
4. The method of claim 1, wherein the polyester prepolymer further comprises a toner, and the mass content of the titanium polyester catalyst in the polyester titanium catalyst composite material system, the mass content of the phosphorus stabilizer and the mass content of the toner are respectively 0.5-20 wt%, 5-15 wt% and 0.5-8 wt%.
5. The DMT process of claim 4, wherein the titanium-based polyester catalyst is Tix(ORO)y(OOC6C4H4COO)zH4Wherein R is C2～C4Z is more than or equal to 1, y + z is 2x +2, x is 4, and the flaky titanium polyester catalyst has a lamellar structure;
the phosphorus stabilizer is more than one of trimethyl phosphate, triethyl phosphate, tripropyl phosphate, triisopropyl phosphate, tributyl phosphate, triphenyl phosphate, tripropyl phosphate, phosphoric acid and phosphorous acid;
the toner is a bluing agent or a reddening agent.
6. The DMT process of claim 5, wherein the polyester titanium based catalyst composite system is prepared by: and (2) melting and blending the solid polyester prepolymer with the polymerization degree of 5-30 with a sheet-shaped titanium polyester catalyst, a phosphorus stabilizer and a toner, and cooling to obtain a polyester titanium catalyst composite material system, wherein the melting and blending temperature is 100-270 ℃, and the time is 1.5-6 hours.
7. The DMT process of claim 5, wherein the polyester titanium based catalyst composite system is prepared by: adding an additive or a dihydric alcohol dispersion liquid of the additive into a polyester prepolymer melt with the polymerization degree of 5-30, uniformly stirring and cooling to obtain a polyester titanium catalyst composite material system, wherein the additive is a sheet-shaped titanium polyester catalyst, a phosphorus stabilizer and a toner, the mass concentration of the dihydric alcohol dispersion liquid of the additive is 30-70 wt%, and the dihydric alcohol is ethylene glycol, 1, 3-propylene glycol or 1, 4-butanediol.
8. The DMT process of claim 5, wherein the polyester titanium based catalyst composite system is prepared by: a, B and C are uniformly mixed and then subjected to esterification reaction, pre-polycondensation reaction and cooling to obtain a polyester titanium catalyst composite material system, wherein A is dibasic acid or dibasic acid ester, B is dihydric alcohol, C is an additive or a dihydric alcohol dispersion liquid of the additive, the additive is a sheet titanium polyester catalyst, a phosphorus stabilizer and a toner, the esterification reaction is carried out in a nitrogen atmosphere, the pressure is 100-400 KPa, the temperature is 180-260 ℃, and the time is 2-2.5 hours; the pressure of the pre-polycondensation reaction is 100-10 KPa, the temperature is 235-270260-270 ℃, and the time is 10-30 min.
9. The DMT process for preparing titanium-based polyester as claimed in claim 8, wherein the molar ratio of the sum of the molar amounts of the diols in B and C to A is 1-2: 1, B is the same as the diol in the diol dispersion of the additive, the mass concentration of the diol dispersion of the additive is 35-70 wt%, and the mass of the flaky titanium-based polyester catalyst is 10-20% of the sum of the mass amounts of the diols in B and C.
10. The DMT process of claim 8, wherein the dibasic acid is terephthalic acid, isophthalic acid or sodium 5-sulfoisophthalate, the dibasic ester is dimethyl terephthalate, and the diol is ethylene glycol, 1, 3-propanediol or 1, 4-butanediol.
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| US6013756A (en) * | 1995-05-23 | 2000-01-11 | Karl Fischer Industrieanlagen Gmbh | Process for producing polyesters using titanium-containing catalyst-inhibitor combinations |
| CN101121777A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Titanium series polyester catalyst |
| CN101235049A (en) * | 2008-03-03 | 2008-08-06 | 东华大学 | Titanium series organic compound material and its preparation and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6013756A (en) * | 1995-05-23 | 2000-01-11 | Karl Fischer Industrieanlagen Gmbh | Process for producing polyesters using titanium-containing catalyst-inhibitor combinations |
| CN101121777A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Titanium series polyester catalyst |
| CN101235049A (en) * | 2008-03-03 | 2008-08-06 | 东华大学 | Titanium series organic compound material and its preparation and application |
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